EP0335484A1 - Procédé de copolymérisation de propylène - Google Patents
Procédé de copolymérisation de propylène Download PDFInfo
- Publication number
- EP0335484A1 EP0335484A1 EP89301131A EP89301131A EP0335484A1 EP 0335484 A1 EP0335484 A1 EP 0335484A1 EP 89301131 A EP89301131 A EP 89301131A EP 89301131 A EP89301131 A EP 89301131A EP 0335484 A1 EP0335484 A1 EP 0335484A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- butene
- catalyst
- propylene
- ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000010936 titanium Substances 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- -1 magnesium halide Chemical class 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 239000004411 aluminium Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003426 co-catalyst Substances 0.000 claims abstract description 5
- 239000011949 solid catalyst Substances 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 32
- 230000035515 penetration Effects 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000004831 Hot glue Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002655 kraft paper Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229920001585 atactic polymer Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RCYUVMCXOQTZOZ-FHQKDBNESA-N (z)-but-2-enedioic acid;2-[2-[2-[4-[(4-chlorophenyl)-phenylmethyl]piperazin-1-yl]ethoxy]ethoxy]ethanol;2-methyl-3-(2-methylphenyl)quinazolin-4-one Chemical compound OC(=O)\C=C/C(O)=O.OC(=O)\C=C/C(O)=O.CC1=CC=CC=C1N1C(=O)C2=CC=CC=C2N=C1C.C1CN(CCOCCOCCO)CCN1C(C=1C=CC(Cl)=CC=1)C1=CC=CC=C1 RCYUVMCXOQTZOZ-FHQKDBNESA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 238000013031 physical testing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
Definitions
- the present invention relates to a process for producing substantially amorphous propylene-butene-1 copolymers.
- US Patent No. 3,923,758 to Carter, Jr. et. al. discloses a high pressure-high temperature solution process for the production of amorphous copolymers of propylene and butene-1 in the presence of a catalyst which is a combination of aluminium trialkyl and titanium trichloride.
- the activity of the catalyst is undesirably low ranging only between about 200 and about 700 kg. polymer/kg. of Ti catalyst/hour resulting in extremely low productivity.
- the equipment and utilities costs are unacceptably high, e.g., because of the required solvent removal and recovery, and of the higher reactor temperature and pressure requirements. In summary, the process is not economically feasible.
- a process for producing substantially amorphous propylene/butene-1 copolymers which comprises reacting from 15 to 90 wt.% propylene and from 85 to 10 wt.% butene-1 at a temperature from 55°C (130°F) to 60°C (140°F) and at a reactor pressure sufficient to maintain the monomers in the liquid phase, in the presence of from 0.7 to 3.0 mol% hydrogen based on the monomer feed to the process and employing as catalyst a composition of:
- all the halides used in forming the catalyst composition are chlorides and all the alkyl groups are ethyl groups.
- the invention will be described hereinafter in connection with the preferred embodiments of the catalyst system; analogous considerations apply to the use of other catalyst systems within the above definition.
- the polymerization can be carried out in a batch reactor, it is preferred to utilize a continuous process to achieve the most random incorporation of the comonomer.
- pressures in the range from 1.5MPa (200 psig) to 3.5MPa (500 psig) are suitable for maintaining the monomers in liquid phase.
- the polymerization is carried out in a stirred reactor at average residence times between about 1 hour and about 3 hours. Sufficient catalyst quantities are fed to the reactor to result in a polymer content in the reactor slurry of from 10 wt.% to 50 wt.%. Especially at the higher end of this range it may be necessary for improved reactor control to add to the reactor from 50 to 100 ppm based on the total monomer feed of an antifoaming agent such as a polydimethylsiloxane.
- an antifoaming agent such as a polydimethylsiloxane.
- the reactor effluent is withdrawn from the reactor, and unreacted monomer and hydrogen is flashed from the product polymer.
- propylene is reacted with from 35 to 45 wt.% butene-1.
- Such a polymer has a particular use as a base polymer in hot melt adhesives.
- the hydrogen is added to the polymerization reactor for control of polymer molecular weight and other properties at concentrations generally about 7 to 10 times the amount conventionally used in the manufacture of isotactic polymer.
- concentration of hydrogen in the total feed to the reaction zone preferably ranges from 1.2 to 2.5 mol%.
- the solid, supported catalyst component should have a molar ratio of magnesium chloride to aluminium chloride of from 8:0.5 to 3.0 and preferably from 8:1.0 to 1.5.
- the molar ratio of magnesium chloride to titanium tetrachloride is from 8:0.1 to 1.0 and preferably from 8:0.4 to 0.6.
- a critical feature of the solid supported catalyst component is that no electron donor compounds should be used in any of the catalyst manufacturing steps. Also, the polymerization process using the catalyst should be carried out in the absence of added electron donors.
- any of the general methods described in US Patents Nos. 4,347,158 and 4,555,496 can be used in preparing the solid supported catalyst component except that these methods must be modified to exclude the use of electron donor compounds.
- the modified method involves co-comminuting magnesium chloride and aluminium trichloride in the absence of an electron donor and then co-comminuting the catalyst support so formed with titanium tetrachloride, also in the absence of an electron donor.
- the solid catalyst component is used in conjunction with a trialkylaluminium co-catalyst, preferably triethylaluminium.
- a trialkylaluminium co-catalyst preferably triethylaluminium.
- the molar ratio of trialkylaluminium co-catalyst to titanium-containing catalyst component i.e., A1/TI ratio, should range from 50:1 to 700:1, preferably from 90:1 to 300:1.
- the specific catalyst used in the process of this invention has the ability to produce propylene units in the polymer with little or no control of the stereochemistry, and also to incorporate butene-1 as randomly as possible to provide maximum disorder in the polymer chain.
- the process is highly efficient and typically results in polymer productions of at least ranging from 4000 to over 20,000 kg polymer/kg Ti catalyst/hour. Also, because of the relatively low temperature and pressure requirements in the process as well as the absence of a solvent recovery step, the process costs, i.e. equipment and utilities costs, are much lower than any prior art process.
- the novel polymer has a low heat of fusion, as determined by Differential Scanning Calorimetry techniques (DSC), an indication of the amorphous nature of the polymer and the lack of significant crystallinity in the polymer structure.
- DSC Differential Scanning Calorimetry techniques
- the polymer contains very low concentrations of catalyst residues, e.g., the total ash content is generally less than about 1000 ppm and the titanium content no more than about 4 ppm and generally less than about 2 ppm.
- additives can be incorporated into the polymer such as antioxidants, U.V. stabilizers and pigments.
- the polymer products of the process of this invention have excellent properties making them useful in a variety of applications, such as blending components for adhesives, caulking and sealing compounds, roofing compositions, and others.
- the important product properties include melt viscosity, ring and ball softening point, needle penetration, and open time.
- the melt viscosity at 190.5°C (375°F) is determined by ASTM test method D-3236 using a Brookfield RVT Viscometer and a No. 27 spindle. Hydrogen is used to control molecular weight and thus melt viscosity.
- the desired viscosity range is between about 1000 and 8000 mPa s at 190.5°C (375°F).
- the polymer should have a viscosity above 5000 mPa s.
- the ring and ball softening point determination is carried out using ASTM E-28 test method.
- the variable affecting the softening point is butene-1 content of the polymer. A decrease in the butene-1 content causes an increase in the ring and ball softening point.
- the preferred range for this property is from 83°C (180°F) to 143°C (290°F).
- Needle penetration is another test which measures the softness of the material at ambient temperature, in this case by the resistance to penetration according to ASTM test method D-1321.
- Butene-1 content affects this property as in the case of ring and ball softening point; however, in this case a decrease in butene-1 content causes a decrease in needle penetration.
- Hot melt adhesive is the open time. This test is an indication of the elapsed time available between adhesive application to kraft paper and bonding of a kraft paper laminate. This is a very important property for the user, as he must know how soon after applying the adhesive he must add the second sheet of paper.
- a polymer sample is heated to 190.5°C (375°F) along with a Bird drawdown applicator. When at temperature, the applicator is placed at the top of the kraft paper and a small puddle of molten polymer is poured near the edge.
- the polymer is drawn into a smooth film, and as soon as the bottom of the paper is reached, a stopwatch is started. At 10-second intervals, pre-cut strips of kraft paper (rough side down transverse machine direction) are placed across the film and pressed into place with a rubber roller. After the last strip is applied, and a subsequent waiting period of 5 minutes, the strips are removed in a smooth, brisk motion.
- the open time is defined as the longest time when 90% or more of the fiber remains bonded. The open times should preferably range from 10 to 60 seconds.
- the experiments were performed in a 1-liter, jacketed autoclave equipped with a magnetically coupled stirrer.
- the temperature of the autoclave was controlled by the use of a mixture of equal weights of glycol and water as the heat transfer fluid flowing through the jacket.
- the temperature of this fluid was controlled by a microprocessor whose temperature indicator was an iron/constantin thermocouple inside the autoclave. With this system, set point temperature could be maintained ⁇ 0.2°C.
- All monomers were polymerization grade, 99.9% pure, and were also passed through molecular sieve beds, as well as beds of copper catalyst for oxygen removal, prior to use. Hydrogen was ultra-high purity, 99.99% and used as is.
- Aluminium alkyl solutions were purchased as 25% W/W in normal heptane and were used as is.
- the solid supported titanium tetrachloride catalyst component had a titanium content of about 2.5 wt.% and was prepared by a modification of the preferred technique disclosed in US Patent No. 4,347,158, i.e., modified only in that all process steps were carried out in the absence of any electron donor components.
- One wt.% solid catalyst slurries were prepared in degassed mineral oil. Prior to each use, the autoclaves were heated to 90°C with a slow nitrogen purge for 30 minutes. After cooling to 30°C, the nitrogen atmosphere was replaced with propylene purge.
- Alkyl solutions and catalyst slurries were prepared in septum vials in dry boxes (nitrogen atmosphere), purged with nitrogen upon removal, and pressurized slightly to avoid contamination. Alkyl solutions and catalyst slurries were introduced into the reactor using hypodermic syringes, previously cleaned with de-ionized water, dried at 120°C, and purged with nitrogen prior to use. 0.68 ml TEA and 0.58 ml of 1% W/W catalyst slurry (2.5% W/W titanium content) were added to the autoclave. Hydrogen was added to the desired partial pressure. Propylene and butene-1 were introduced using a sight gauge and nitrogen pressure. The reactor content was heated to 60°C (140°F) and maintained while stirring at 500 rpm. After 1 hour, the temperature was lowered and excess monomers were vented. The propylene/butene-1 copolymer was dried under vacuum at 100°C overnight.
- a polymer was prepared in a large scale continuous pilot plant operation, wherein monomers, hydrogen and catalyst components were separately and continuously charged to a stirred reactor, the total monomer feed rate corresponding to about a 2-hour residence time in the reactor.
- the organoaluminium compound of the catalyst system was a heptane solution of triethylaluminum (TEA).
- TAA triethylaluminum
- the solid supported titanium tetrachloride catalyst component was of the same type as that of Examples 1-4, but it was pumped into the reactor as a 6 wt% mixture in petrolatum. The two catalyst components were added at rates directly proportional to the polymer production rates and in amounts sufficient to maintain the polymer solids concentration in the reactor slurry at about 20.5%.
- the catalyst productivity (1b polyer/1b of Ti catalyst component) was calculated from the polymer slurry withdrawal rate, solids content in the slurry, and the titanium catalyst addition rate.
- the product polymer was separated from unreacted monomer, stabilized with Isonox R 129 and then subjected to testing. Table 2 summarizes the pertinent operating conditions and the results of physical testing. TABLE 2 Example No.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT89301131T ATE82988T1 (de) | 1988-03-30 | 1989-02-06 | Propylencopolymerisationsverfahren. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17500688A | 1988-03-30 | 1988-03-30 | |
US175006 | 1988-03-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0335484A1 true EP0335484A1 (fr) | 1989-10-04 |
EP0335484B1 EP0335484B1 (fr) | 1992-12-02 |
Family
ID=22638446
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89301131A Expired - Lifetime EP0335484B1 (fr) | 1988-03-30 | 1989-02-06 | Procédé de copolymérisation de propylène |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0335484B1 (fr) |
JP (1) | JP2679735B2 (fr) |
KR (1) | KR0132581B1 (fr) |
CN (1) | CN1040005C (fr) |
AT (1) | ATE82988T1 (fr) |
AU (1) | AU601606B2 (fr) |
CA (1) | CA1308857C (fr) |
DE (1) | DE68903660T2 (fr) |
ES (1) | ES2044081T3 (fr) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0422498A2 (fr) * | 1989-10-06 | 1991-04-17 | MITSUI TOATSU CHEMICALS, Inc. | Copolymères de butène-1 |
EP0475306A1 (fr) * | 1990-09-07 | 1992-03-18 | Rexene Products Company | Procédé pour la préparation d'homopolymères amorphes élastomères de propylene |
US5266641A (en) * | 1989-10-06 | 1993-11-30 | Mitsui Toatsu Chemicals, Inc. | Butene-1 copolymers and resin compositions containing the same |
WO1994005711A1 (fr) * | 1992-09-08 | 1994-03-17 | Rexene Corporation | Copolymeres de 1-butene/propylene amorphes a haute resistance a la traction |
DE4323233A1 (de) * | 1993-07-12 | 1995-01-19 | Huels Chemische Werke Ag | Verfahren zur Herstellung von amorphen oder wenig kristallinen Co- oder Terpolymeren aus Olefinen |
EP0659778A1 (fr) * | 1993-12-17 | 1995-06-28 | ENICHEM ELASTOMERI S.r.l. | Catalyseur pour la préparation de copolymères élastomères d'éthylène et de propylène |
US5681913A (en) * | 1992-09-08 | 1997-10-28 | Rexene Corporation | High tensile strength amorphous 1-butene/propylene and ethylene/propylene copolymers |
WO2006108744A1 (fr) * | 2005-04-13 | 2006-10-19 | Degussa Gmbh | Polyolefine fortement visqueuse et largement amorphe |
WO2006108747A1 (fr) * | 2005-04-13 | 2006-10-19 | Degussa Gmbh | Utilisation d'une polyolefine tres visqueuse, essentiellement amorphe, dans la fabrication d'une pellicule |
US7807768B2 (en) | 2005-04-13 | 2010-10-05 | Evonik Degussa Gmbh | Highly viscous, largely amorphous polyolefin |
CN112041408A (zh) * | 2018-04-20 | 2020-12-04 | 宝洁公司 | 用于吸收制品的粘合剂组合物 |
EP3868797A1 (fr) * | 2020-02-13 | 2021-08-25 | Korea Petrochemical Ind. Co., Ltd. | Copolymère de polypropylène amorphe et son procédé de préparation |
US11505719B2 (en) | 2018-04-20 | 2022-11-22 | The Procter & Gamble Company | Adhesive composition for absorbent articles |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR8902210A (pt) * | 1988-05-12 | 1990-01-02 | Union Carbide Corp | Processo para a copolimerizacao de pelo menos dois comonomeros,propileno e etileno |
FI104824B (fi) * | 1997-06-24 | 2000-04-14 | Borealis As | Menetelmä propeenin terpolymeerien aikaansaamiseksi |
DE10031293B4 (de) * | 1999-09-01 | 2008-03-06 | Evonik Degussa Gmbh | Verfahren zur Herstellung von weitgehend amorphen Poly-alpha-Olefinen |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0135358A1 (fr) * | 1983-08-12 | 1985-03-27 | Mitsui Petrochemical Industries, Ltd. | Copolymères statistiques de butène-1 |
EP0251771A1 (fr) * | 1986-06-30 | 1988-01-07 | REXENE PRODUCTS COMPANY (A Delaware Corporation) | Polymères de propylène et leur préparation |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4736002A (en) * | 1986-06-30 | 1988-04-05 | El Paso Products Company | Novel propylene polymerization process |
-
1988
- 1988-07-07 CA CA000571363A patent/CA1308857C/fr not_active Expired - Lifetime
- 1988-07-14 AU AU19058/88A patent/AU601606B2/en not_active Ceased
- 1988-09-21 JP JP63235110A patent/JP2679735B2/ja not_active Expired - Lifetime
- 1988-12-23 KR KR1019880017321A patent/KR0132581B1/ko not_active IP Right Cessation
-
1989
- 1989-02-06 ES ES89301131T patent/ES2044081T3/es not_active Expired - Lifetime
- 1989-02-06 AT AT89301131T patent/ATE82988T1/de not_active IP Right Cessation
- 1989-02-06 DE DE8989301131T patent/DE68903660T2/de not_active Expired - Lifetime
- 1989-02-06 EP EP89301131A patent/EP0335484B1/fr not_active Expired - Lifetime
- 1989-02-25 CN CN89101155A patent/CN1040005C/zh not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0135358A1 (fr) * | 1983-08-12 | 1985-03-27 | Mitsui Petrochemical Industries, Ltd. | Copolymères statistiques de butène-1 |
EP0251771A1 (fr) * | 1986-06-30 | 1988-01-07 | REXENE PRODUCTS COMPANY (A Delaware Corporation) | Polymères de propylène et leur préparation |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0627464A3 (fr) * | 1989-10-06 | 1995-02-22 | Mitsui Toatsu Chemicals | Copolymères de butène-1 et compositions résineuses contenant ces copolymères. |
EP0422498A3 (en) * | 1989-10-06 | 1992-11-25 | Mitsui Toatsu Chemicals, Incorporated | Butene-1 copolymers and resin compositions containing the same |
US5206324A (en) * | 1989-10-06 | 1993-04-27 | Mitsui Toatsu Chemicals, Inc. | Butene-1 copolymer and resin composition containing the same |
US5266641A (en) * | 1989-10-06 | 1993-11-30 | Mitsui Toatsu Chemicals, Inc. | Butene-1 copolymers and resin compositions containing the same |
EP0627464A2 (fr) * | 1989-10-06 | 1994-12-07 | Mitsui Toatsu Chemicals, Incorporated | Copolymères de butène-1 et compositions résineuses contenant ces copolymères |
EP0422498A2 (fr) * | 1989-10-06 | 1991-04-17 | MITSUI TOATSU CHEMICALS, Inc. | Copolymères de butène-1 |
EP0475306A1 (fr) * | 1990-09-07 | 1992-03-18 | Rexene Products Company | Procédé pour la préparation d'homopolymères amorphes élastomères de propylene |
CN1044123C (zh) * | 1990-09-07 | 1999-07-14 | 雷克斯尼产品公司 | 非晶态弹性丙烯均聚物的制备方法 |
WO1994005711A1 (fr) * | 1992-09-08 | 1994-03-17 | Rexene Corporation | Copolymeres de 1-butene/propylene amorphes a haute resistance a la traction |
US5302675A (en) * | 1992-09-08 | 1994-04-12 | Rexene Corporation | High tensile strength amorphous 1-butene/propylene copolymers |
US5681913A (en) * | 1992-09-08 | 1997-10-28 | Rexene Corporation | High tensile strength amorphous 1-butene/propylene and ethylene/propylene copolymers |
US5714554A (en) * | 1992-09-08 | 1998-02-03 | Rexene Corporation | High tensile strength amorphous 1-butene/propylene and ethylene/propylene copolymers |
DE4323233A1 (de) * | 1993-07-12 | 1995-01-19 | Huels Chemische Werke Ag | Verfahren zur Herstellung von amorphen oder wenig kristallinen Co- oder Terpolymeren aus Olefinen |
EP0659778A1 (fr) * | 1993-12-17 | 1995-06-28 | ENICHEM ELASTOMERI S.r.l. | Catalyseur pour la préparation de copolymères élastomères d'éthylène et de propylène |
CN1050613C (zh) * | 1993-12-17 | 2000-03-22 | 埃尼凯姆·埃拉斯托麦里公司 | 制备弹性乙烯-丙烯共聚物的催化剂及其应用 |
WO2006108744A1 (fr) * | 2005-04-13 | 2006-10-19 | Degussa Gmbh | Polyolefine fortement visqueuse et largement amorphe |
WO2006108747A1 (fr) * | 2005-04-13 | 2006-10-19 | Degussa Gmbh | Utilisation d'une polyolefine tres visqueuse, essentiellement amorphe, dans la fabrication d'une pellicule |
US20080214757A1 (en) * | 2005-04-13 | 2008-09-04 | Evonik Degussa Gmbh | Use of a Highly Viscous Largely Amorphous Polyolefin For the Production of a Film |
US7807768B2 (en) | 2005-04-13 | 2010-10-05 | Evonik Degussa Gmbh | Highly viscous, largely amorphous polyolefin |
US8288489B2 (en) * | 2005-04-13 | 2012-10-16 | Evonik Degussa Gmbh | Use of a highly viscous largely amorphous polyolefin for the production of a film |
CN112041408A (zh) * | 2018-04-20 | 2020-12-04 | 宝洁公司 | 用于吸收制品的粘合剂组合物 |
US11505719B2 (en) | 2018-04-20 | 2022-11-22 | The Procter & Gamble Company | Adhesive composition for absorbent articles |
EP3868797A1 (fr) * | 2020-02-13 | 2021-08-25 | Korea Petrochemical Ind. Co., Ltd. | Copolymère de polypropylène amorphe et son procédé de préparation |
Also Published As
Publication number | Publication date |
---|---|
AU601606B2 (en) | 1990-09-13 |
CN1040005C (zh) | 1998-09-30 |
CA1308857C (fr) | 1992-10-13 |
JP2679735B2 (ja) | 1997-11-19 |
DE68903660T2 (de) | 1993-05-19 |
ES2044081T3 (es) | 1994-01-01 |
CN1036213A (zh) | 1989-10-11 |
JPH01249816A (ja) | 1989-10-05 |
DE68903660D1 (de) | 1993-01-14 |
ATE82988T1 (de) | 1992-12-15 |
KR0132581B1 (ko) | 1998-04-13 |
AU1905888A (en) | 1989-10-05 |
EP0335484B1 (fr) | 1992-12-02 |
KR890014590A (ko) | 1989-10-24 |
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